Anthraquinone compounds



Patented Dec. 18, 1945- UNITED STATES PATENT OFFICE" j ANTHRAQUINONE'COMPOUNDS Joseph B. Dickey and John R. Byers, Jr., Rochester, N. Y.,assignors to Eastman Kodak Company, Rochester, N. Y., a corporation ofNew Jersey No Drawing. Application July 13, 1944, Serial No. 544,811

4 Claims.

This invention relates to anthraquinone compounds for textilescontaining cellulose carboxylic ester rayon, and to a process for thepreparation of such dyes.

The anthraquinone compound of the following formula:

(I? OH O O NH has long been known. This compound, however, is of littlevalue as a dye for textiles containing cellulose carboxylic ester rayon,because it colors such textile materials only very poorly from anaqueous suspension of the compound. On the other hand, the anthraquinonecompounds of the following general formula:

t O NHR R=a1kyl, such as methyl or ethyl which are also known, readilydye such textiles violet shades. The dyed textiles, however, have poorresistance to gas-fading.

Still another known anthraquinone compound having the formula:

aforesaid prior compounds. It is, accordingly, an object of ourinvention to providenew anthraquinone dyes and to provide a process forpreparing such dyes. Other objects will become apparent hereinafter.

Our new anthraquinone compounds can be represented by the followinggeneral formula:

G 1 t' t NH-Q,-0-D(OD),.OR'

wherein n represents a positive integer of from 1 to 2, D represents anethylene group, a trimethylene group or a propylene group, R representsa member selected from the group consisting of hydrogen and an alkylgroup containing from 1 to 2 carbon atoms, Q represents a phenylenegroup (e. g. o-phenylene and p-phenylene groups) which may carrysubstituents, such as halogen,

an acetamino group,.a methyl group, a hydroxyl group, etc., Z and Z eachrepresents a member selected from the group consisting of hydrogen and ahydroxyl group.

Our new dye having the formula:

constitutes an improvement over the known dye having the formula:

on o o NHOO-CHz-ClIr-OH in that it requires about twice as much of theknown dye to obtain a fabric of the same shade as can be obtained withour new dye. Yet our new dye is fully as fast to light and as resistantto gas-fading as is the known dye. our new dye has a dyeing speed about33 per cent greater than does the known dye.

In accordance with our invention we prepare our new anthraquinonecompounds by condensing quinizarin (1, fl-dihydroxyanthraquinone),1,4,5-trihydroxyanthraquinone, 1,4,8-trihydroxyanthraquinone or1,4,5,8-tetrahydroxyanthraquinone (each in admixture with at least percent by weight of the corresponding leuco compound) with an aminocompound of the following general 1 formula:

HzN-Q-O-D- (O-D) n-O-R wherein n represents a positive integer of from 1to 2, Q represents a phenylene group which may necessarily, carried outin the presence of an acid-condensing agent, e. g. boric acid,phosphoric acid, sulfuric acid, hydrochloric acid, stannous chloride,stannic chloride, etc. Borio acid is advantageously employed. Thecondensations are also advantageously, but not necessarily, carried outin a medium or diluent which is inert with respect to the condensation.Alcohols, especially alcohols of the formula: CnH2n+1 wherein nrepresents a positive integer of from 2 to 4 are advantageously employedas the diluent. Tetrahydrofurfuryl alcohol or pyridine can be employedas the diluent.

The hydroxy anthraquinone compound, used as a starting material, isadvantageously dispersed in the diluent by-means of a dispersing agent,e. g. a sodium salt of a sulfonated oleic acid ester. Heat acceleratesthe condensations.

Following the condensation, the leuco compound is oxidized in any of theknown manners of oxidizin leuco compounds, e. g. by passing air throughthe reaction mixture or preferably. by means of an oxidizing agent, suchas sodium perborate. I

The following examples will serve to illustrate our new anthraquinonecompounds and the manner of obtaining the same.

- Example 1. 1-Hydro:ty-#{pJBJp-hgldroxyethoxy) -ethoxyl -anilino}-anthraquinone 9.6 g. (0.04 mole) of quinizarin, 2.64 g. (0.011 mole) ofleucoquinizarin, 6 g. of boric acid, 9.8 g. (0.05 mole) ofp-[p-(B-hydroxyethoxy) -ethoxylaniline and 50 g. of ethyl alcohol wererefluxed together for hours on a steam bath. 3 g. of sodium perboratedissolved in cc. of water were then added to the reaction mixture tooxidize the leuco compound. The reaction mix-.

hydroxyethoxy)-ethoxyl anilino} anthraquinone (melting at 120 to 140C.), 1-hydroxy-4- {o-chloro-p [p-(p-hydroxyethoxy) ethoxylanilino}anthraquinone, l-hydroxy-4-{p-[7-(yhydroxypropoxy) -propoxyl -anilino}anthraquihydroxyethoxy) -ethoxyl -anilino} -a.nthraquinone can beprepared.

Example 2.-1 Hydroxy 4 {p- [fl-(pethoaryethoxyl-ethozcy]-anilino}-anthraqinone 9.6 g. (0.04 mole) ofquinizarin, 2.64 g. (0.011 mole) of leucoquinizarin, 6 g. of boric acid,11g. (0.05 mole) of p-[fi-(p-ethoxyethoxy) -ethoxylaniline and g. ofethyl alcohol were refluxed together for about 20 hours on a steam bath..3 g. of sodium perborate dissolved in 25 cc. of water were then addedto the reaction mixture .to oxidize the leuco compound. The reactionmixture was then cooled to about 25 C. and the above formulated dye wasfiltered off. The dye was washed with ethyl alcohol and then with water.To remove excess quinizarin, the wet dye was placed in 375 cc. of watercontaining 28 g. of sodium hydroxide and the mixture was brought to aboil. The resulting slurry was filtered hot, and the resulting blue. dyewas washed with hot water untilfree from alkali. The yield was 14 g. Thedye melted at 90 to 105 C.

In a similar manner, 1-hydroxy-4-{p-[p-(fimethoxyethoxy) ethoxyl-anilino} anthraquinone can be prepared.

Example 3.1,5,8 Trihgdroxy -4 -{p lp-(p-hydromyethoxy) -ethowyl-anilino}-anthraquinone H0 0 on t 110 0 NH 0- HTCHTOCHT'CHI'OH 10.88 g.(0.04 mole) of l,4,5,8-tetrahydroxy anthraquinone, 3.01 g. (0.01 mole)of leuco-' 1,4,5,8-tetrahydroxy-anthraquinone and 6 g. of boric acidwere placed in 50 cc. of isopropanol. The mixture was heated toboilingunder reflux and while boiling was continued, 9.8 g. (0.05 mole)of p-[p-(c-hydroxyethoxy)-eth0xyl-aniline dissolved in 25 cc. ofisopropanol were added dropwise, with stirring, over a period of 10hours.

Stirring and boiling were continued for 10 hours after the addition. 3g. of sodium perborate dissolved in 25 cc. of water were then added tothe reaction mixture to oxidize the leuco compound. The reaction mixturewas then cooled, whereupon the above formulated dye crystallized out. Itwas filtered off, washed with ethyl alcohol and then with water. .To'remove excess 1,4,5,8-tetrahydroxyanthraquinone, the wet dye was broughtto a boil in 3'75 cc. of water containing 28 g. of sodium hydroxide. Theresulting slurry was filtered hot and the resulting blue dye was washedwith hot water until free from alkali. The dy melted at to C. i

r In a similar manner, 1,5,8-trihydroxy-4-{o-[p- .none and1,5,8-trihydroxy-4-{c-chloro-p- ['v-l' sents'a'positive integer of from1 to 2, and B reprehydroxypropoxy) -propoxy] o-'anilino}-.anthraquinoneand 1,5-dihydroxy-4-{p-[p-tB-hydroxyethoxy)-ethoxy]-anilino}-anthraquinone can be prepared.

Example 4.1 -Hydr:vy-4- p- {s- [p- (,B-hydroxyethowy)-ethoa:yl-etho:z:y} anilino anthraquinone H OH or i 0 0 9.6 g. (0.04mole) of quinizarin, 2.64 g. (0.011 mole) of leucoquinizarin, 6 g. ofboric acid, 12 g. (0.05 mole) of p {18 [p (,8 hydroxyethoxy) ethoxyl-ethoxy}-aniline and 5.0 g. of ethyl alcohol were refluxed together forabout 20 hours on a steam bath. 3 g. of sodium perborate dissolved incc. of water were then added to the reaction mixture to oxidize theleuco compound. The reaction mixture was then cooled to about 25 C. andthe above formulated dye was filtered off. The dye was washed with ethylalcohol and then with water. To remove excess quinizarin, the wet dyewas placed in 375 cc. of water containing 28 g. of sodium hydroxide andthe resulting mixture was brought to a boil. The resulting slurry wasfiltered hot, and the blue dye was washed with hot Water until free fromalkali. The dye melted at 115 to 120 C.

In a similar manner, 4- p{fi-[,B-(fi-ethoxy ethoxy) -ethoxy]-ethoxy}-anilino anthraquinone can be prepared.

The aniline derivatives of the following formula:

wherein n represents a positive integer of from 1 to 2, Q represents aphenylene group, D represents an ethylene group, a trimethylene group ora propylene group and R represents an alkyl group of from 1 to 2 carbonatoms can be prepared by condensing a chloronitrobenzene derivative ofthe following formula:

wherein Q represents a phenylene group which may carry substituents suchas halogen, an acetamino group, a methyl group or a hydroxyl group,etc., with a sodium alcoholate of the following formula:

wherein D represents an ethylene group, a trimethylene group or apropylene group, n represents a positive integer of from 1 to 2, and Rrepresents hydrogen or an alkyl group containing from 1 to 2 carbonatoms, and then reducing the resulting nitro compound with hydrogen, inthe presence of a nickel catalyst, especially of the Raney type, inmethanol, at from 80 to 100 C. in an autoclave under a hydrogen pressureof 400 to 1800 pounds per square inch. The initial condensation of thechloronitro compound and the sodium alcoholate is advantageously carriedout at 90 to 100 C. for about 20 hours. The sodium alcoholates can beprepared by adding sodium to the alcohols of the formula:

wherein D represents an ethylene group, a trimethylene group or apropylene group, n represents hydrogen 3.01. an alkyl group of from '1to 2 carbon atoms. Many of these alcohols are very well known substancesand readily available on the market, e. g. diethylene glycol andtriethylene glycol and the monomethyl and monoethyl ethers of theseglycols. Dipropylene glycol is also available on the market.Tripropylene glycol can be prepared by reacting 10 moles of dipropyleneglycol with one mole of sodium and condensing the resulting mixture withone mole of propylene chlorohydrin, Di-trimethylene glycol. can be pre-.pared by reacting .10 moles of trimethylene glycol with one mole ofsodium and condensing the re: sulting mixture with trimethylenechlorohydrin. Tri-trimethylene glycol canlbe prepared byreacting 10moles o1 di-trimethYlene glycol with one mole of sodium and condensingthe resulting mixture with one mole of trimethylene chlorohydrin. Themonomethyl and monoethyl ethers of diand tri-propylene glycol and ofdi-trimethylene glycol and tri-trimethylene glycol can be prepared byreacting 5 to 10 moles of the glycol with sodium and condensing theresulting" mixture with methyl iodide or ethyl iodide.

The anthraquinone dyes of our invention are especially useful for thecoloration of organic derivatives of cellulose which include thehydrolyzed, as well as the unhydrolyzed, cellulose carboxylic esters,such as cellulose acetate, cellulose propionate and cellulose butyrate,and the hydrolyzed, as well as the unhydrolyzed, mixed carboxylic estersof cellulose, such as cellulose acetate-propionate and celluloseacetate-butyrate, and the cellulose ethers, such as methyl cellulose,ethyl cellulose and benzyl cellulose. Our new dyes are also useful forthe coloration of cellulose esters and cellulose ether lacquers, as wellas lacquers made from polyvinyl compounds. Our new dyes can be used tocolor nylons and textiles prepared therefrom.

The anthraquinone dyes of our invention can be applied to the colorationof fabrics made of or containing organic derivatives of cellulose, suchas cellulose acetate rayon, by the known dyeing or printing methods. Inaccordance with the known dispersion method of dyeing, the anthraquinonedyes are first ground to a fine powder, intimately mixed with a suitabledispersing or solubilizing agent, following which the resulting mixtureis added. to water or a dilute solution of soap in water to form anaqueous dye bath. The textile materials are then immersed in such a dyebath in accordance with known procedures. Suitable dispersing orsolubilizing agents include soap, sulforicinoleic acid, the alkali metalsalts of sulforicinoleic acid, sulfonated oleic, stearic or palmiticacid or salts thereof, such as the sodium or ammonium salts. Forprinting, our new dyes are advantageously ground with a suitabledispersing agent, such as a sodium lignin sulfonate and the resultingprintin mixture is then applied to the textile materials, in accordancewith known printing methods.

In accordance with the recommendations of Chemical Abstracts, the termpropylene is intended to mean the group having the following formula:

and the term trimethylene is intended to mean the group having thefollowing. formula:

What we claim and desire to be secured by'Letters Patent of the UnitedStates is:

1. The anthraquinone compounds'having 'the following general formula: r4

I 0 i v w z' t NH- -0-D- 0-D),.-o-R wherein n represents a. positiveinteger of from 1 to 2, Q represents a phenylene group, D represents a.member selected from the group consisting of ethylene, -trimethylene andpropylene groups, R represents a member selected from the groupconsisting of hydrogen and an alkyl group containing from 1 to 2 carbonatoms, and Z and Z' each represents a, member selected from the groupconsisting of hydrogen and a hydroxyl group. V

2. The. anthraquinone compound having the following formula:

g on i NEGO-CHz-CHr-O-GIIa-CHrOH -,-3. The anthraquinone compound havingthe following formula:

NHO-o-cHrcnro-cm-cm-ocmn 4. The anthraquinone compound having thefollowing formula:

NH-OO-CHrCHrO-CHr-CHrOH JOSEPH B. DICKEY. JOHN R. BYERS, JR.

